Computational Study of the Interactions between Benzene and Crystalline Ice Ih: Ground and Excited States |
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| Authors: | Dr Divya Sharma Dr W M C Sameera Dr Stefan Andersson Prof Gunnar Nyman Prof Martin J Paterson |
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| Institution: | 1. Institute of Chemical Sciences, School of Engineering and Physical Sciences, Edinburgh, United Kingdom;2. Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto, Japan;3. University of Gothenburg, Department of Chemistry and Molecular Biology, Gothenburg, Sweden;4. SINTEF Materials and Chemistry, Trondheim, Norway |
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| Abstract: | Ground‐state geometries of benzene on crystalline ice cluster model surfaces (Ih) are investigated. It is found that the binding energies of benzene‐bound ice complexes are sensitive to the dangling features of the binding sites. We used time‐dependent DFT to study the UV spectroscopy of benzene, ice clusters, and benzene–ice complexes, by employing the M06‐2X functional. It is observed that the size of the ice cluster and the dangling features have minor effects on the UV spectral characteristics. Benzene‐mediated electronic excitations of water towards longer wavelengths (above 170 nm) are noted in benzene‐bound ice clusters, where the cross‐section of photon absorption by water is negligible, in good agreement with recent experimental results (Thrower et al., J. Vac. Sci. Technol. A, 2008, 26 , 919–924). The intensities of peaks associated with water excitations in benzene–ice complexes are found to be higher than in isolated ice clusters. The π→π* electronic transition of benzene in benzene–ice complexes undergoes a small redshift compared with the isolated benzene molecule, and this holds for all benzene‐bound ice complexes. |
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| Keywords: | bond energy density functional calculations electronic structure molecular modeling surface chemistry |
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